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You searched for subject:(copper pyrazolate complexes). One record found.

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Florida International University

1. Shi, Kaige. New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks.

Degree: PhD, Chemistry, 2018, Florida International University

The main objectives of this project are the synthesis and redox- or photo-active modification and CO2 adsorption studies of metal-organic frameworks (MOFs) based on Cu3-pyrazolate secondary building units (SBUs). Trinuclear copper(II) complexes of the formula [Cu33-O)(µ-4-R-pz)3X3]z have been studied extensively due to their redox, magnetic and catalytic properties. In earlier work, we have shown that trinuclear copper(II) complexes of the formula [Cu33-O)(µ-4-R-pz)3X3]z pz = pyrazolato anion; R = H, CH(O), Cl, Br and NO2; X = Cl, NCS, CH3COO, CF3COO and pyridine – can be oxidized to the corresponding z+1, formally CuII2CuIII, species. In this project, fourteen (14) new copper-pyrazolate complexes of varying nuclearities (Cu3, Cu6, Cu7 and Cu12), terminal ligands (-NO2, py, -N3, -Cl) and bridging ligands (4-Cl-pzH and 4-Ph-pzH) have been synthesized. Efforts have been made to prepare MOFs based on the Cu33-O)-SBUs. While attempting to design the most suitable SBU for redox-active MOF construction, it was found that the one-electron oxidation of the all-CuII complex [Cu33-O)(µ-pz)3(NO2)3]2–, [8]2-, was achieved at redox potential more cathodic than any other Cu33-O)-complexes studied in our laboratory. The mixed-valent compound, [Cu33-O)(µ-pz)3(NO2)3], [8]-, the easiest accessible CuII2CuIII species known to date, was characterized spectroscopically. Compound [8] and analogous [11] release NO almost quantitatively upon the addition of PhSH or acetic acid. The system is catalytic in the presence of excess nitrite. Before embarking on the study of photo-active MOFs, a simpler model compound – a dimer of trimer [{Cu33-OH)(µ-4-Cl-pz)3(py)2}2(µ-abp)](ClO4)4 [21], where abp = 4,4’-azopyridine, was synthesized and its photochemistry was studied. The absorption spectra recorded before and after irradiation indicated a structural change. Two dimensional (2D) and three dimensional (3D) materials with {[Cu33-OH)(µ-4-R-pz)3]2+}n SBUs where R = Ph or Cl , which can potentially undergo cis/trans-isomerization, have been prepared during this project. A Phenyl substituent at 4-position on the pyrazole ligand leads to the formation of new class of 2D sheets. Three new 3D porous MOFs based on {[Cu33-OH)(µ-4-Cl-pz)3]2+}n SBUs have interpenetrated- lattice structures and are capable of adsorbing CO2Advisors/Committee Members: Raphael G Raptis, Konstantinos Kavallieratos, Yuk-Ching Tse-Dinh, Jaroslava Miksovska, Chunlei (Peggy) Wang.

Subjects/Keywords: copper pyrazolate complexes; electrochemistry; MOFs; Gas adsorption; Chemistry; Physical Sciences and Mathematics

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Shi, K. (2018). New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks. (Doctoral Dissertation). Florida International University. Retrieved from https://digitalcommons.fiu.edu/etd/3859 ; FIDC007044

Chicago Manual of Style (16th Edition):

Shi, Kaige. “New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks.” 2018. Doctoral Dissertation, Florida International University. Accessed August 21, 2019. https://digitalcommons.fiu.edu/etd/3859 ; FIDC007044.

MLA Handbook (7th Edition):

Shi, Kaige. “New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks.” 2018. Web. 21 Aug 2019.

Vancouver:

Shi K. New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks. [Internet] [Doctoral dissertation]. Florida International University; 2018. [cited 2019 Aug 21]. Available from: https://digitalcommons.fiu.edu/etd/3859 ; FIDC007044.

Council of Science Editors:

Shi K. New Polynuclear Copper-Pyrazolate Complexes: Towards the Synthesis of Photo- and Redox-Active Metal Organic Frameworks. [Doctoral Dissertation]. Florida International University; 2018. Available from: https://digitalcommons.fiu.edu/etd/3859 ; FIDC007044

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